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CN101528814A - Process for production of modified conjugated diene polymers, modified conjugated diene polymers produced by the process, rubber compositions, and tires - Google Patents

Process for production of modified conjugated diene polymers, modified conjugated diene polymers produced by the process, rubber compositions, and tires Download PDF

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Publication number
CN101528814A
CN101528814A CNA2007800398479A CN200780039847A CN101528814A CN 101528814 A CN101528814 A CN 101528814A CN A2007800398479 A CNA2007800398479 A CN A2007800398479A CN 200780039847 A CN200780039847 A CN 200780039847A CN 101528814 A CN101528814 A CN 101528814A
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conjugated diene
diene polymer
modified conjugated
compound
rubber
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CN101528814B (en
Inventor
田中健
真崎孝二
小泽洋一
铃木英寿
克莉丝汀·M·拉德梅彻
泰伦斯·E·霍根
曾根卓男
松本贵臣
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Yinnenshi Materials Co ltd
Bridgestone Corp
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Bridgestone Corp
JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

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  • Medicinal Chemistry (AREA)
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  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention provides a process for producing a modified conjugated diene based polymer which attains favorable interaction between a rubber component and carbon black and/or silica, thereby improving dispersibility of the fillers, and which exhibits excellent properties such as heat-buildup-suppressing performance, fracture characteristics, and wear resistance; a modified conjugated diene based polymer produced through the process; a rubber composition containing the diene polymer; and a tire produced from the rubber composition and exhibiting the above properties. The process for producing a modified conjugated diene based polymer includes a step (a) of reacting a silicon compound with a conjugated diene based polymer having an active end so that the reaction takes place at the active end, the silicon compound having a protected primary amino group in the molecule thereof and a bi-functional silicon atom to which a hydrocarbyloxy group and a reactive group including a hydrocarbyloxy group are bonded, to thereby modify the active end, and a step (b) of performing condensation reaction which involves the compound having a bi-functional silicon atom, in the presence of a titanium compound serving as a titanium-based condensation-accelerating agent.

Description

The manufacture method of modified conjugated diene polymer, the modified conjugated diene polymer, rubber combination and the tire that obtain by this method
Technical field
The modified conjugated diene polymer, rubber combination and the tire that the present invention relates to a kind of manufacture method of modified conjugated diene polymer, obtain by this method.Say in further detail, the modified conjugated diene polymer that relates to a kind of manufacture method of modified conjugated diene polymer, obtains by this method, its rubber combination and the tire that uses said composition to form with following characteristic, the interaction excellence of the rubber constituent of the manufacture method of this modified conjugated diene polymer and carbon black and/or silicon-dioxide, can improve excellences such as the dispersiveness of these weighting agents, low exothermicity, destruction characteristic, antifriction consumption, simultaneously the quality stability excellence.
Background technology
In recent years, follow the social desirability of saving the energy and the attention degree of environmental problem is improved, enabled global carbonic acid gas and discharged rule, meanwhile require the low fuel-fee of automobile further.In order to tackle such requirement, tyre performance also requires to reduce rotary resistance.As the method that reduces the tyre rotation resistance,, generally use the method for the low material of exothermicity as rubber combination although in the method for tire construction optimization, also study.
In order to obtain the low rubber combination of such exothermicity, so far, carry out mostly silicon-dioxide and carbon black as the technological development of the rubber combination of weighting agent with modified rubber.Wherein, following effective ways have especially been proposed: utilize and to contain the method (for example, with reference to patent documentation 1 or 2) of the polymerization activity end of the conjugated diene polymer that obtains by the anionoid polymerization of using organolithium being carried out modification with the alkoxyl silicone alkane derivatives of the interactional functional group of weighting agent.
Yet these rubber combinations are applicable to mostly can guarantee the active polymkeric substance of polymer ends, may not be abundant to the modified effect that is combined with silicon-dioxide and sooty rubber combination.In addition, method of modifying is owing to can not fully add side chain to main chain mostly at present, and when reality was used, cold flow became bigger harm, and when carrying out the part coupling in order to tackle this, existence certainly will reduce the problem of modified effect.
Therefore, in order to overcome above-mentioned shortcoming, further to improve modified effect, proposed when using organoalkoxysilane that the reactive terminal of conjugated diene polymer is carried out modification, the method of interpolation condensation accelerator (for example in reaction system, patent documentation 3), yet,, also insufficient to the low loss effect of carbon black filled material though this rubber combination has improved the low loss effect to silica-based packing material.
Patent documentation 1: the special fair 6-53763 communique of Japan
Patent documentation 2: the special fair 6-57767 communique of Japan
Patent documentation 3:WO03/087171 brochure
Summary of the invention
Invent problem to be solved
Under such situation, the objective of the invention is to, the modified conjugated diene polymer that a kind of manufacture method of modified conjugated diene polymer is provided, obtains by this method, its rubber combination and the tire that uses said composition to form with following characteristic, the interaction excellence of the rubber constituent of the manufacture method of this modified conjugated diene polymer and carbon black and/or silicon-dioxide, can improve the dispersiveness of these weighting agents, excellences such as low exothermicity, destruction characteristic, antifriction consumption.
The method that is used to deal with problems
The inventor etc. inquire in order to achieve the above object repeatedly, found that: by comprising following two operations: the reactive terminal that makes conjugated diene polymer has the operation of compound reaction carrying out modified-reaction that intramolecularly has the amino of specific structure and is combined in 2 functionality Siliciumatoms of the-oxyl on the Siliciumatom at least with comprising; And in the presence of the condensation accelerator that comprises specific titanium compound, the operation of carrying out condensation reaction.Can address the above problem.
The present invention is based on that above-mentioned opinion finishes.
(1) a kind of manufacture method of modified conjugated diene polymer, it is characterized in that it has following operation: (a) make this reactive terminal of the conjugated diene polymer with reactive terminal and primary amino be protected in intramolecularly and comprise 1-oxyl and 1 reactive group is combined in the compound reaction of 2 functionality Siliciumatoms on the same Siliciumatom and the operation of carrying out modification; And (b) the titanium that comprises titanium compound be condensation accelerator in the presence of, comprise the operation of the condensation reaction that the compound of aforementioned 2 functionality Siliciumatoms participates in.
(2) in addition; manufacture method according to above-mentioned (1) described modified conjugated diene polymer; it also has following operation: (c) to the group reactive terminal that is combined in conjugated diene polymer, that come the compounds of the self-contained 2 functionality Siliciumatoms processing that is hydrolyzed, the protected primary amino in this group is converted to the deprotection operation of free amine group.
(3) according to the manufacture method of above-mentioned (1) or (2) described modified conjugated diene polymer, the compound that comprises 2 functionality Siliciumatoms that uses in (a) operation is by the silicon compound of general formula (I) expression, by the silicon compound of general formula (II) expression and the silicon compound of being represented by general formula (III).
[Chemical formula 1]
Figure A20078003984700071
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
[Chemical formula 2]
Figure A20078003984700081
(in the formula, R 7～R 11The alkyl of representing carbonatoms 1～20 independently of one another, R 12The alkyl of the divalent of expression carbonatoms 1～12.)
[chemical formula 3]
Figure A20078003984700082
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the R of the divalent of expression carbonatoms 1～12 13Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
(4) according to the manufacture method of above-mentioned (3) described modified conjugated diene polymer, the A in the general formula (I) is the-oxyl of halogen atom or carbonatoms 1～20.
(5) according to the manufacture method of each described modified conjugated diene polymer of above-mentioned (1)～(4), conjugated diene polymer with reactive terminal is to be polymerization starter with the organic alkali metal compound, makes conjugated diene compound separately or makes conjugated diene compound and the aromatic series vinyl compound carries out anionoid polymerization and obtains.
(6) according to the manufacture method of above-mentioned (5) described modified conjugated diene polymer, conjugated diene compound is for being selected from 1,3-butadiene, isoprene and 2, in 3-dimethyl-1,3-butadiene at least a kind.
(7) according to the manufacture method of above-mentioned (5) or (6) described modified conjugated diene polymer, aromatic ethenyl compound is a vinylbenzene.
(8) according to the manufacture method of each described modified conjugated diene polymer of above-mentioned (5)～(7), the content of the polymerized unit of aromatic ethenyl compound is 0～55 quality % of conjugated diene polymer, and the vinyl bonds content of this conjugated diene polymer is 7～65 quality % of the polymerized unit of conjugated diolefine.
(9) according to the manufacture method of each described modified conjugated diene polymer of above-mentioned (1)～(8), the condensation accelerator that (b) uses in the operation is at least a kind in the alkoxide, carboxylate salt and the methyl ethyl diketone complex salt that are selected from titanium or their mixing salt.
(10) a kind of modified conjugated diene polymer is characterized in that, it obtains by each described manufacture method of above-mentioned (1)～(9).
(11) a kind of rubber combination is characterized in that, comprises above-mentioned (10) described modified conjugated diene polymer.
(12) according to above-mentioned (11) described rubber combination, it comprises the rubber constituent of the aforementioned modified conjugated diene polymer more than the 15 quality % with respect to 100 mass parts, comprises the silicon-dioxide and/or the carbon black that amount to 20～120 mass parts.
(13) according to above-mentioned (12) described rubber combination, rubber constituent constitutes by a kind in the multipolymer of the vinylbenzene that is selected from natural rubber, synthetic synthetic polyisoprene, divinyl rubber, styrene-butadiene rubber(SBR), ethene-alpha-olefin copolymer rubber, ethene-alpha-olefin-diene copolymer rubber, chloroprene rubber, halogenated butyl rubber and band halogenation methyl of the modified conjugated diene polymer of 15～100 quality % and 85～0 quality % and iso-butylene at least.
(14) a kind of pneumatic tyre is characterized in that, its each described rubber combination of use above-mentioned (11)～(13).
(15) a kind of pneumatic tyre is used for each described rubber combination of above-mentioned (11)～(13) at any position of tyre surface, tread base and sidewall portion.
The invention effect
Utilize the present invention, the modified conjugated diene polymer that a kind of manufacture method of modified conjugated diene polymer can be provided, obtain by this method, its rubber combination and the tire that uses said composition to form with following characteristic, the interaction excellence of the rubber constituent of the manufacture method of this modified conjugated diene polymer and carbon black and/or silicon-dioxide, can improve the dispersiveness of these weighting agents, excellences such as low exothermicity, destruction characteristic, antifriction consumption, and quality stability excellence.
Embodiment
The manufacture method of modified conjugated diene polymer of the present invention has following operation: (a) make this reactive terminal of the conjugated diene polymer with reactive terminal and primary amino be protected in intramolecularly and comprise 1-oxyl and 1 reactive group is combined in compound (below, the be sometimes referred to as alkoxysilane compound containing trialkylsilyl group in molecular structure) reaction of 2 functionality Siliciumatoms on the same Siliciumatom and the operation of carrying out modification; And (b) the titanium that comprises titanium compound be condensation accelerator in the presence of, the operation of carrying out the condensation reaction that aforementioned 2 functionality silicon compounds participate in.
In addition, usually, after the reactive terminal interpolation alkoxysilane compound containing trialkylsilyl group in molecular structure of conjugated diene polymer carries out modified-reaction, before condensation reaction, add condensation accelerator, also can be before adding alkoxysilane compound containing trialkylsilyl group in molecular structure behind (before the modified-reaction) interpolation condensation accelerator, add alkoxysilane compound containing trialkylsilyl group in molecular structure and carry out modified-reaction, carry out condensation reaction then.
The conjugated diene polymer with reactive terminal that uses in the method for the present invention can be obtained or also can be obtained with other monomer copolymerizations by the independent polymerization of diene monomer, its manufacture method is not particularly limited, can use the arbitrary method in solution polymerization process, gaseous polymerization, the mass polymerization, especially the preferred solution polymerization.In addition, polymerized form can be in compartment and the continous way any.
In addition, the metal that is present in the reactive site in the molecule of conjugated diene polymer is preferably selected from a kind in the alkalies and alkaline earth, preferred as alkali, especially preferred lithium metal.
In the above-mentioned solution polymerization process, by for example making organic alkali metal compound, especially making lithium compound as polymerization starter, with conjugated diene compound separately or conjugated diene compound and aromatic ethenyl compound carry out anionoid polymerization, thereby polymkeric substance that can manufacturing objective.
And then there is the Halogen monomer in mixing, makes the halogen atom sensitization in the polymkeric substance by organometallic compound also is effective.For example, make and comprise iso-butylene unit, p-methylstyrene unit and also be effective to the bromine part lithiumation of the multipolymer of brooethyl styrene units and as reactive site.
As above-mentioned conjugated diene compound, can list for example 1,3-butadiene; Isoprene; 1.3-pentadiene; 2,3-dimethyl-1,3-butadiene; 2-phenyl-1,3-butadiene; 1,3-hexadiene etc.These can use separately, two or more uses also capable of being combined, and in the middle of these, preferred especially 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
In addition, the aromatic ethenyl compound as being used for these conjugated diene compound copolymerization can list for example vinylbenzene; Alpha-methyl styrene; The 1-vinyl naphthalene; The 3-Vinyl toluene; Vinyl xylene, ethyl vinyl benzene: Vinylstyrene; 4-phenylcyclohexane ethene; 2,4,6-Three methyl Benzene ethene etc.These can use separately, use more than two kinds also capable of being combined, special optimization styrenes in the middle of these.
And then, use conjugated diene compound and aromatic ethenyl compound to carry out under the situation of copolymerization as monomer, from obtaining practicality aspects such as monomeric easy degree and anionoid polymerization characteristic is aspect excellences such as activity etc., especially preferably use 1,3-butadiene and vinylbenzene respectively.
In addition, using under the situation of solution polymerization process, the monomer concentration in the solvent is preferably 5～50 quality %, more preferably 10～30 quality %.In addition, using conjugated diene compound and aromatic ethenyl compound to carry out under the situation of copolymerization, the content that adds the aromatic ethenyl compound in the monomer mixture is preferably the scope of 0～55 quality %.
The lithium compound of polymerization starter is not particularly limited, preferred hydrocarbyl lithium and the acid amides lithium compound of using, before use under the situation of person's hydrocarbyl lithium, can obtain polymerization and begin end and have that alkyl and another are terminal to be the conjugated diene polymer at polymerization activity position.In addition, under the situation of the acid amides lithium compound that uses the latter, can obtain polymerization and begin that end has nitrogen-containing group, another terminally is the conjugated diene polymer at polymerization activity position.
As above-mentioned hydrocarbyl lithium, the hydrocarbyl lithium that preferably has the alkyl of carbonatoms 2～20, can list the reaction product of lithium ethide for example, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, uncle's octyl group lithium, positive decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl phenyl lithium, 4-phenyl butyl lithium, cyclohexyl lithium, cyclopentyl lithium, di isopropenylbenzene and butyllithium etc., especially preferred n-Butyl Lithium in the middle of these.
On the other hand, as the acid amides lithium compound, can list for example hexa-methylene imide li, tetramethyleneimine lithium, piperidines lithium, heptamethylene imide li, ten dimethylene imide lis, dimethylformamide lithium, diethylamide lithium, dibutyl acid amides lithium, dipropyl acid amides lithium, diheptyl acid amides lithium, dihexyl acid amides lithium, dioctyl acid amides lithium, two-2-ethylhexyl acid amides lithium, didecyl acid amides lithium, positive methylpiperazine lithium, ethyl propyl acid amides lithium, ethyl-butyl acid amides lithium, Ethylbenzyl acid amides lithium, methylbenzene buserelin lithium etc.From with the viewpoint of sooty repercussion effect and polymerization initiating power, cyclic amide lithiums such as preferred hexa-methylene imide li, tetramethyleneimine lithium, piperidines lithium, heptamethylene imide li, ten dimethylene imide lis in the middle of these, preferred especially hexa-methylene imide li and tetramethyleneimine lithium.
Usually can be used for polymerization and modulate these acid amides lithium compounds modulate the material that forms in advance by secondary amine and lithium compound, also can modulation in (in-situ, original position) in polymerization system.In addition, the usage quantity of this polymerization starter is preferably selected in the scope that with respect to monomer 100g is 0.2～20 mmole.
Use aforementioned lithium compound to be not particularly limited, can use existing known method as polymerization starter, the method for making conjugated diene polymer by anionoid polymerization.
Specifically, state before use under the existence of the randomizer that lithium compound uses as polymerization starter, as required, by making conjugated diene compound or conjugated diene compound and aromatic ethenyl compound in hydrocarbon system solvents such as the organic solvent of reactionlessness, for example aliphatics, alicyclic, aromatic hydrocarbon compound, carry out anionoid polymerization, thereby obtain the conjugated diene polymer of target.
As aforementioned hydrocarbon system solvent, the hydrocarbon of preferred carbonatoms 3～8 can list for example propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, hexanaphthene, propylene, 1-butylene, iso-butylene, trans 2-butylene, cis 2-butylene, 1-amylene, 2-amylene, 1-hexene, 2-hexene, benzene,toluene,xylene, ethylbenzene etc.These can use separately, also can mix more than two kinds and use.
In addition, the randomizer of Shi Yonging is to have the microstructure of control conjugated diene polymer, for example control 1 of divinyl part in the butadiene-styrene copolymer as required, the compound of effects such as the composition distribution of the monomeric unit in the increase of 3,4 keys in 2 keys, the isoprene copolymer etc. or the conjugated diene compound-aromatic vinyl copolymer, the butadiene unit in for example butadiene-styrene copolymer, the randomization of styrene units.This randomizer is not particularly limited, and can suitably select any compound the known compound of existing randomizer from being used as usually.Specifically, can list dimethoxy benzene, tetrahydrofuran (THF), glycol dimethyl ether, Diethylene Glycol dibutyl ether, diethylene glycol dimethyl ether, 2, two (2-the tetrahydrofuran (THF))-propane of 2-, triethylamine, pyridine, positive methylmorpholine, N, N, N ', N '-Tetramethyl Ethylene Diamine, 1, the ethers of 2-two pyrimidine ethane etc. and tertiary amines etc.In addition, can also use sodium salt classes such as sylvite classes such as tertiary amine potassium, potassium tert.-butoxide, tertiary amine sodium.
These randomizer can be used alone, also use more than two kinds capable of being combined.In addition, its usage quantity is preferably being selected in the scope of 0.01～1000 molar equivalent for 1 mole with respect to lithium compound.
Temperature in this polyreaction preferably 0～150 ℃, more preferably select in 20～130 ℃ the scope.Polyreaction can be carried out under generation pressure, and expectation is to operate under the sufficient pressure that monomer is remained substantially liquid phase usually.That is, pressure depends on each material that is aggregated, used polymerisation medium and polymerization temperature, and expectation can be used higher pressure, and such pressure can make appropriate means acquisitions such as reactor pressurization by utilizing rare gas element in polyreaction.
Reactions such as in this polymerization, all raw material expectation use that polymerization starter, solvent, monomer etc. are relevant with polymerization has removed and anhydrated, oxygen, carbonic acid gas, protic compound hinder the material of material.
In addition, use polymkeric substance as elastomeric situation under, the second-order transition temperature that the polymkeric substance of gained or multipolymer are tried to achieve by differential thermal analysis (Tg) is preferably-95 ℃～-15 ℃.By making second-order transition temperature, can obtain to suppress viscosity and uprise, handle easy polymkeric substance in above-mentioned scope.
Among the present invention; at first, make the reactive terminal of the above-mentioned conjugated diene polymer that makes and primary amino be protected in intramolecularly and comprise 1-oxyl and 1 reactive group is combined in the compound reaction of 2 functionality Siliciumatoms on the same Siliciumatom and carries out modified-reaction.
Be protected in intramolecularly and comprise 1-oxyl and 1 reactive group is combined in the compound (being designated hereinafter simply as " properties-correcting agent ") of 2 functionality Siliciumatoms on the same Siliciumatom as primary amino, can list for example general formula (I), general formula (II) and general formula (III).
[chemical formula 4]
Figure A20078003984700151
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
[chemical formula 5]
Figure A20078003984700152
(in the formula, R 7～R 11The alkyl of representing carbonatoms 1～20 independently of one another, R 12The alkyl of the divalent of expression carbonatoms 1～12.)
[chemical formula 6]
Figure A20078003984700153
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the R of the divalent of expression carbonatoms 1～12 13Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
In the above-mentioned formula (I)～(III), be the object lesson of the univalent alkyl of carbonatoms 1～20 independently respectively, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, various amyl groups, various hexyls, various octyl groups, various decyls, various dodecyls, various tetradecyls, various hexadecyls, various octadecyls, various heneicosyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl group, hexenyl, octenyl, cyclopentenyl, cyclohexenyl, phenyl, tolyl, xylyl, naphthyl, benzyl, styroyl, menaphthyl etc.Wherein, the methyl of preferred carbonatoms 1～4, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., more preferably ethyl, methyl, the tertiary butyl.
Alkyl as the divalent of carbonatoms 1～12 can list the alkylidene group of carbonatoms 1～12, the arylidene of carbonatoms 6～12, the arylidene alkylene of carbonatoms 7～12 etc.
Above-mentioned carbonatoms 1～12 alkylidene group can be any in straight chain shape, the chain, specifically, can list a catenate alkylidene group such as straight chain shape alkylidene groups such as methylene radical, ethylidene, trimethylene, tetramethylene, hexa-methylene, eight methylene radical, decamethylene, propylidene, isopropylidene, isobutylene, 2-methyl trimethylene, isopentylidene, isohexylidene, different octylene, 2-ethyl hexylidene, isodecyl thiazolinyl.
Arylidene as carbonatoms 6～12, can list for example phenylene, methylphenylene, dimethyl phenylene, naphthylidene etc., as the arylidene alkylene of carbonatoms 7～12, can list for example phenylene methylene radical, phenylene ethylidene, xylylene etc.Wherein, the alkylidene group of preferred carbonatoms 1～4, preferred especially trimethylene.
The-oxyl of the preferred halogen atom of the reactive group of A, carbonatoms 1～20 as halogen atom, can list fluorine, chlorine, bromine, iodine, wherein preferred chlorine.
As the-oxyl of carbonatoms 1～20, can list the alkoxyl group of carbonatoms 1～20, the allyloxy of carbonatoms 6～20, the aralkoxy of carbonatoms 7～20 etc.
Alkoxyl group as above-mentioned carbonatoms 1～20, can list methoxyl group, oxyethyl group, positive propoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, various hexyloxy, various octyloxy, various last of the ten Heavenly stems oxygen base, various dodecyloxy, various tetradecyloxyaniline, various n-Hexadecane oxygen base, various octadecane oxygen base, each heneicosane oxygen base etc.As the allyloxy of carbonatoms 6～20, can list for example phenoxy group, methylphenoxy, dimethyl phenoxy, naphthyloxy etc.,, for example can list benzyloxy, benzene oxyethyl group, naphthalene methoxyl group etc. as the aralkoxy of carbonatoms 7～20.The alkoxyl group of preferred carbonatoms 1～4 in the middle of these, preferred especially oxyethyl group.
As other reactive groups, can list the group that contains carboxyl, acid anhydrides residue, each glyoxalidine quinoline base, N-Methyl pyrrolidone base, isocyanate group etc.
In addition, the R of formula (I) 3, R 4And R 5Both combinations, can form 4～7 yuan of rings with they institute's bonded Siliciumatoms, same, the R of formula (II) 9, R 10And R 11Both combinations, can form 4～7 yuan of rings with they institute's bonded Siliciumatoms.As these 4～7 yuan of rings, can list the material of methylene radical with carbonatoms 4～7.
As comprising the compound that has protected primary amine groups at least and be combined in 2 functionality Siliciumatoms of the alkoxyl group on the Siliciumatom; can list for example N; two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-; N; two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-; N; two (trimethyl silyl) amino-ethyl methyl dimethoxysilanes of N-; N, two (trimethyl silyl) amino-ethyl methyldiethoxysilane of N-; and 1-trimethyl silyl-2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene etc.
In addition, as aforementioned A is the compound of halogen atom, for example can list, N, two (trimethyl silyl) aminopropyl methyl methoxy base chlorosilanes of N-, N, two (trimethyl silyl) aminopropyl methyl ethoxy chlorosilanes of N-, N, two (trimethyl silyl) amino-ethyl methyl methoxy base chlorosilanes of N-, N, two (trimethyl silyl) amino-ethyl methyl ethoxy chlorosilanes of N-etc.
Preferred N, two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-, N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-, 1-trimethyl silyl-2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene.
These properties-correcting agent can use a kind separately, also can make up use more than 2 kinds.In addition, this properties-correcting agent can be partial condensate.
Here, partial condensate is meant a part (non-whole) SiOSi be combined into by condensation of the SiOR of properties-correcting agent.
In the above-mentioned modified-reaction, the polymer chain of employed polymkeric substance preferred at least 10% has activity.
Living polymerization chain end, for example P -Li +The reaction of the properties-correcting agent during with general formula (I) f=1 can be represented by following reaction formula.In addition, P represents (being total to) polymer chain of conjugated diene compound or conjugated diene compound and aromatic ethenyl compound.
[chemical formula 7]
Figure A20078003984700181
Figure A20078003984700191
Similarly, living polymerization chain end, for example P -Li +Can represent by following reaction formula with the reaction of the properties-correcting agent of general formula (II).
[chemical formula 8]
Figure A20078003984700192
In the modified-reaction of above-mentioned properties-correcting agent, the usage quantity of this properties-correcting agent is preferably 0.5～200mmol/kg conjugated diene polymer.With content 1～100mmol/kg conjugated diene polymer more preferably, be preferably 2～50mmol/kg conjugated diene polymer especially.Here, conjugated diene polymer be meant during fabrication or make after do not contain the independent quality of polymkeric substance of the additives such as antiaging agent that added.Usage quantity by making properties-correcting agent is in above-mentioned scope, the excellent dispersion of weighting agent, and the mechanical characteristics after the sulfuration, antifriction consumption, low exothermicity improve.
In addition, the addition means of above-mentioned properties-correcting agent is not particularly limited, and can list the method for once adding, the method that gradation is added or the method for adding continuously etc., preferred method of once adding.
In addition, properties-correcting agent can be combined in polymerization to begin end, polymerization and stops in end, main polymer chain, the side chain any, hang down the viewpoint of exothermicity from the inhibition energy from polymer ends disappearance, improvement, preferred properties-correcting agent is directed to polymerization and begins end or polymerization termination end.
Among the present invention,, use specific condensation accelerator for the condensation reaction that above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure participated in that promotes to use as above-mentioned properties-correcting agent.
Condensation accelerator used herein can add before above-mentioned modified-reaction, preferably behind modified-reaction and condensation reaction begin preceding interpolation.Under the situation of before modified-reaction, adding, can cause and the direct reaction of reactive terminal, exist-oxyl can not be directed to the problem of reactive terminal.
In addition, under the situation that begins to add the back in condensation reaction, the problem that exists the inhomogeneous dispersion of condensation accelerator, catalyst performance to reduce.
As the interpolation period of condensation accelerator, usually after modified-reaction begins 5 minutes～5 hours, preferably after modified-reaction begins 15 minutes～1 hour.
The condensation accelerator that uses in (b) of the present invention operation preferably uses alkoxide, carboxylate salt and the acetylacetonate complex of titanium (Ti).
As concrete condensation accelerator, can list four (2-ethyls-1, the 3-hexylene glycol) titanium, four (2-methyl isophthalic acids, the 3-hexylene glycol) titanium, four (2-propyl group-1, the 3-hexylene glycol) titanium, four (2-butyl-1, the 3-hexylene glycol) titanium, four (1, the 3-hexylene glycol) titanium, four (1, the 3-pentanediol) titanium, four (2-methyl isophthalic acids, the 3-pentanediol) titanium, four (2-ethyls-1, the 3-pentanediol) titanium, four (2-propyl group-1, the 3-pentanediol) titanium, four (2-butyl-1, the 3-pentanediol) titanium, four (1, the 3-heptanediol) titanium, four (2-methyl isophthalic acids, the 3-heptanediol) titanium, four (2-ethyls-1, the 3-heptanediol) titanium, four (2-propyl group-1, the 3-heptanediol) titanium, four (2-butyl-1, the 3-heptanediol) titanium, four (2-Ethylhexyl Alcohol) titanium, tetramethyl alcohol titanium, titanium tetraethoxide, four n-propyl alcohol titaniums, titanium tetraisopropylate, four propyl carbinol titaniums, four propyl carbinol titanium oligomers, four titanium isobutoxides, four sec-butyl alcohol titaniums, four trimethyl carbinol titaniums, two (oleic acid) two (2 ethyl hexanoic acid) titanium, two (triethanolamineization) two titanium propanolates, two (triethanolamineization) two butanols titaniums, stearic acid three butanols titaniums, stearic acid three titanium propanolates, methyl ethyl diketone three titanium propanolates, two (methyl ethyl diketone) two titanium propanolates, (ethyl acetoacetic acid) three titanium propanolates, two (ethyl acetoacetic acid) titanium propanolates of methyl ethyl diketone, methyl ethyl diketone three butanols titaniums, two (methyl ethyl diketone) two butanols titaniums, ethyl acetoacetic acid three butanols titaniums, two (ethyl acetoacetic acid) butanols titaniums of methyl ethyl diketone, four (methyl ethyl diketone) titanium, two (ethyl acetoacetic acid) diacetyl acetone titanium, two (2 ethyl hexanoic acid) titanium oxide, two (laurate) titanium oxide, two (cycloalkanes acid esters) titanium oxide, two (stearate) titanium oxide, two (oleic acid ester) titanium oxide, two (linoleate) titanium oxide, four (2 ethyl hexanoic acid) titanium, four (lauric acid) titanium, four (naphthenic acid) titanium, four (stearic acid) titanium, four (oleic acid) titanium, four (linolic acid) titanium, (two-2,4-diacetylmethane) two propyl carbinol titaniums, two (stearate) titanium oxide, two (dipivaloylmethane) titanium oxide, two (diacetylmethane) titanium oxide, four (lactic acid) titanium etc.Wherein, preferred four (2-ethyl-1,3-hexylene glycol) titanium, four (2-Ethylhexyl Alcohol) titanium, (two-2,4-diacetylmethane) two propyl carbinol titaniums.
As the usage quantity of this condensation accelerator, the mole number of above-claimed cpd is preferably 0.1～10, is preferably 0.5～5 especially with respect to the mol ratio that is present in the-oxyl total amount in the reaction system.Usage quantity by making condensation accelerator can be carried out condensation reaction effectively in above-mentioned scope.
Condensation reaction among the present invention is preferably carried out in the aqueous solution, preferred 85～180 ℃ of the temperature during condensation reaction, further preferred 100～170 ℃, preferred especially 110～150 ℃.
Temperature when making condensation reaction can be carried out condensation reaction effectively and finish up to reaction in above-mentioned scope, can suppress degradation problem under the quality that the aging reaction etc. of the polymkeric substance that changes in time of resulting modified conjugated diene polymer causes.
In addition, condensation reaction time be generally 5 minutes～10 hours, be preferably 15 minutes～about 5 hours.By making condensation reaction time, can successfully finish condensation reaction in above-mentioned scope.
In addition, the pressure of the reaction system during condensation reaction is generally 0.01～20MPa, preferred 0.05～10MPa.
The form of condensation reaction is not particularly limited, and can use batch reactor, also can use devices such as multistage flow reactor to carry out with continous way.In addition, can also carry out this condensation reaction and desolventizing simultaneously.
From the amino of the properties-correcting agent of modified conjugated diene polymer of the present invention can be protected, also can be transformed into primary amine by deprotection, arbitrary situation all is preferred.As carry out deprotection and handle, then can use following order.
That is,, become free amino by the silyl protecting group on this protection amino is hydrolyzed.Handle by it being carried out desolventizing, thus the polymkeric substance of exsiccant that obtains having primary amine groups.In addition, from comprising stage that this condensation handles up to desolventizing and arbitrary stage of dry polymer can will be carried out deprotection as required from the protection primary amine groups of properties-correcting agent and be handled.
Among the present invention; as described above carry out condensation and handle after; further implement (c) deprotection operation; to the group reactive terminal that is combined in conjugated diene polymer, that come the compounds of the self-contained 2 functionality Siliciumatoms processing that is hydrolyzed; make protected primary amine groups in this base become the amino of radical, can obtain the modified conjugated diene polymer of target thus.
Mooney viscosity (the ML of the modified conjugated diene polymer that obtains among the present invention 1 + 4, 100 ℃) be preferably 10～150, more preferably 15～100.Value by making mooney viscosity is in above-mentioned scope, can obtain the rubber combination of the mechanical characteristics excellence after mixing operability and the sulfuration.
In the rubber combination of the present invention,, preferably comprise the above-mentioned modified conjugated diene polymer of 15 quality % at least as rubber constituent.The more preferably content of this modified conjugated diene polymer in the rubber constituent is more than the 30 quality %, is preferably especially more than the 40 quality %.By making the modified conjugated diene polymer in the rubber constituent is more than the 15 quality %, can obtain to have the rubber combination of the rerum natura of expectation.
This modified conjugated diene polymer can use a kind, also use more than 2 kinds capable of being combined.In addition, as other rubber constituents that are used in combination with this modified conjugated diene polymer, can list natural rubber, synthetic synthetic polyisoprene, divinyl rubber, styrene-butadiene rubber(SBR), ethene-alpha-olefin copolymerization rubber, ethene-alpha-olefin-diene copolymerization rubber, acrylonitrile-butadiene copolymerization rubber, chloroprene rubber, halogenated butyl rubber and these mixtures etc.In addition, can also use its part for multifunctional type, for example have a material of branched structure by tin tetrachloride, the such properties-correcting agent of silicon tetrachloride.
Rubber combination of the present invention preferably contains as the silicon-dioxide of weighting agent and/or carbon black.
Above-mentioned silicon-dioxide is not particularly limited, and can select arbitrarily from using the habitual material of weighting agent as the enhancing of existing rubber.
As silicon-dioxide, can enumerate for example wet silicon dioxide (moisture silicic acid), dry type silicon-dioxide (silicic anhydride), Calucium Silicate powder, pure aluminium silicate etc., wherein, preferably take into account the wet silicon dioxide of the most pronounced effects of improving effect and anti-slippery of destruction characteristic.
Be not particularly limited as carbon black, use for example SRF, GPF, FEF, HAF, ISAF, SAF etc., preferred bromine adsorptive capacity (IA) is more than the 60mg/g and dibutyl phthalate oil number (DBP) is the above carbon black of 80ml/100g.By using carbon black, the effect of improving of sliding capability and anti-destruction characteristic improves, HAF, ISAF, the SAF of preferred especially wear resistant excellence.
Silicon-dioxide and/or carbon black can use a kind, also use more than 2 kinds capable of being combined.
Silicon-dioxide and/or carbon black preferably cooperate 20～120 mass parts with respect to rubber constituent 100 mass parts, from the viewpoint of improving effect of enhancing property and each characteristic of bringing thus, and then preferred 25～100 mass parts.By the amount that makes carbon black and/or silicon-dioxide is above-mentioned scope, and industrial operation excellences such as mixing operability can obtain the destruction characteristic as the expectation of rubber combination.
In the rubber combination of the present invention, as strengthening, can also cooperate silane coupling agent according to the purpose that further improves its enhancing property and low exothermicity with under the situation of weighting agent at silicon-dioxide.
As this silane coupling agent; can list for example two (3-triethoxysilylpropyltetrasulfide) tetrasulfides; two (3-triethoxysilylpropyltetrasulfide) trisulphide; two (3-triethoxysilylpropyltetrasulfide) disulphide; two (2-triethoxysilyl ethyl) tetrasulfide; two (3-trimethoxy-silylpropyl) tetrasulfide; two (2-trimethoxysilylethylgroup group) tetrasulfide; 3-sulfydryl propyl trimethoxy silicane; 3-sulfydryl propyl-triethoxysilicane; 2-mercaptoethyl Trimethoxy silane; 2-mercaptoethyl triethoxyl silane; 3-trimethoxy-silylpropyl-N; N-dimethyl thiocarbamyl tetrasulfide; 3-triethoxysilylpropyltetrasulfide-N; N-dimethyl thiocarbamyl tetrasulfide; 2-triethoxysilyl ethyl-N; N-dimethyl thiocarbamyl tetrasulfide; 3-trimethoxy-silylpropyl benzothiazolyl tetrasulfide; 3-triethoxysilylpropyltetrasulfide benzothiazolyl tetrasulfide; 3-triethoxysilylpropyltetrasulfide methacrylic ester list sulfide; 3-trimethoxy-silylpropyl methacrylic ester list sulfide; two (3-diethoxymethyl silyl propyl group) tetrasulfide; 3-sulfydryl propyl group dimethoxy-methyl silane; dimethoxy-methyl silyl propyl group-N; N-dimethyl thiocarbamyl tetrasulfide; dimethoxy-methyl silyl propylbenzene benzothiazolyl tetrasulfide etc.; from improve strengthening the viewpoint of property effect etc., preferred two (3-triethoxysilylpropyltetrasulfide) polysulfides and 3-trimethoxy-silylpropyl benzothiazolyl tetrasulfides in the middle of these.
These silane coupling agents can use a kind separately, use more than 2 kinds also capable of being combined.
In the rubber combination of the present invention, as rubber constituent, use and to have imported polymer-modified with the high functional group of the affinity of silicon-dioxide at the molecular activity position, therefore, the use level of silane coupling agent can be than usually still less.The use level of preferred silane coupling agent changes according to the kind of silane coupling agent etc., preferably selects in the scope that with respect to silicon-dioxide is 1～20 quality %.During this quantity not sufficient 1 quality %, be difficult to give full play to the effect of coupling agent, in addition, surpass the gelation that 20 quality % then may cause rubber constituent.From the effect of coupling agent and prevent viewpoints such as gelation, the preferred use level of this silane coupling agent is the scope of 5～15 quality %.
In the scope of not damaging the object of the invention, can in rubber combination of the present invention, add common various chemical reagent, for example vulcanizing agent, vulcanization accelerator, process oil, antiaging agent, antiscorch(ing), zinc oxide, stearic acid etc. as required in the use of rubber industry circle.
In addition, rubber combination of the present invention get by using open mixing roll, Banbury etc. such as roller mixing rolls such as closed mixing machine being mixing, is shaped to vulcanize after processing, applicable to various rubber items.For example, based on tire purposes such as tire tread, tread base, carcass, sidewall, bead part, can also be used for purposes such as vibration-proof rubber, splash pan, belt, flexible pipe and other industrial goods, especially, be suitable for the tyre surface rubber balance excellence, that hang down combustion expense tire, outsize tire, high-performance tire of making low exothermicity, antifriction consumption, strength at break.
Embodiment
Below, by embodiment the present invention is specifically described, but the present invention is not subjected to any qualification of these embodiment.In addition, the various mensuration among the embodiment is undertaken by following method.
(1) uses as a servant diolefine contents of ethylene partly altogether
(with respect to diolefine sub-population %)
According to 270MHz 1H-NMR tries to achieve.
(2) combined styrene content (the quality % in the polymkeric substance)
According to 270MHz 1H-NMR tries to achieve.
(3) weight-average molecular weight
Use gel permeation chromatography (GPC) (East ソ one society's system, HLC-8220GPC), try to achieve with polystyrene conversion.
(4) mooney viscosity (ML 1+4, 100 ℃)
According to JI S K6300,, try to achieve under 100 ℃ of 4 minutes working rotor times, temperature L rotor, preheating 1 minute.
(5) evaluation of physical property of vulcanized rubber
The rerum natura of vulcanized rubber can by following (a) and (b) method measure.
(a) tan δ (50 ℃): tan δ (50 ℃) use U.S. レ オ メ ト リ Star Network ス society system spectrometer, under the dynamic deformation 1% that stretches, frequency 10Hz, 50 ℃ condition, measure.With exponential representation, numerical value is big more, and rotary resistance is more little, good more.
(b) antifriction consumption (blue Berne abrasion index): using blue Berne type abrasion trier, is that 25% abrasion scale shows that in addition, the mensuration temperature is a room temperature with sliding ratio.Index is big more, the antifriction consumption is good more.
Synthesizing of＜properties-correcting agent 〉
Synthesis example 1:N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-synthetic
Under nitrogen atmosphere; add the 3-aminopropyl methyldiethoxysilane (Gelest corporate system) of 36g among the dichloromethane solvent 400ml in glass flask as the aminosilane position with stirrer; in solution, add trimethylsilyl chloride (Aldrich corporate system) 48ml then again as the protection position; triethylamine 53ml; at room temperature stirred 17 hours; then by being placed on evaporation reaction solution on the vaporizer; remove and desolvate; obtain reaction mixture; again the reaction mixture that obtains is carried out underpressure distillation under the condition of 665Pa; obtain the N of 40g, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-as 130～135 ℃ of cuts.
Synthesizing of synthesis example 2:1-trimethyl silyl-2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene
Except use 28g 2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene as aminosilane position, 24ml trimethylsilyl chloride as the protection position; with synthesis example 1 is that benchmark carries out, and obtains 1-trimethyl silyl-2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene.
Synthesizing of synthesis example 3:3-(2,2,5,5-tetramethyl-(1-azepine-2,5-two silicon pentamethylene)-1-yl)-propyl group methyldiethoxysilane
Except using 44ml 1,2-pair-(chloro-dimetylsilyl)-ethane (Gelest corporate system) is that benchmark carries out as beyond the protection position with synthesis example 1; obtain 3-(2,2,5; 5-tetramethyl-(1-azepine-2,5-two silicon pentamethylene)-1-yl)-the propyl group methyldiethoxysilane.
Synthesis example 4:N, two (trimethyl silyl) aminopropyl dimethylethoxysilane of N-synthetic
Except using 30g 3-aminopropyl dimethylethoxysilane (Gelest corporate system) as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (trimethyl silyl) aminopropyl dimethylethoxysilane of N-.
Synthesizing of synthesis example 5:N-methyl-N-(trimethyl silyl) aminopropyl methyldiethoxysilane
Except use 33g N-methyl-3-aminopropyl methyldiethoxysilane [record based on Organic letters (2002) 4 (13) 2117～2119 is synthetic] as the aminosilane position, use the 24ml trimethylsilyl chloride as the protection position; with synthesis example 1 is that benchmark carries out, and obtains N-methyl-N-(trimethyl silyl) aminopropyl methyldiethoxysilane.
Synthesis example 6:N, N-dimethyl-3-aminopropyl methyldiethoxysilane synthetic
Record based on TOHKEMY 2003-155381 is synthesized.
Synthesis example 7:N, two (trimethyl silyl) aminopropyltriethoxywerene werene of N-synthetic
Under nitrogen atmosphere; add the 3-aminopropyltriethoxywerene werene (Gelest corporate system) of 41g among the dichloromethane solvent 400ml in the glass flask that possesses stirrer as the aminosilane position; and then in solution, add as trimethylsilyl chloride (Aldrich corporate system) 48ml that protects the position; triethylamine 53ml; at room temperature stirred 17 hours; then by being placed on evaporation reaction solution on the vaporizer; remove and desolvate; obtain anabolic reaction solution; under the 5mm/Hg condition, resulting reaction soln is carried out underpressure distillation again; thereby obtain the N of 125～130 ℃ of cuts, two (trimethyl silyl) the aminopropyltriethoxywerene werene 40g of N-.
Synthesis example 8:N, two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-synthetic
Except using 31.5g 3-aminopropyl methyl dimethoxysilane as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-.
Synthesis example 9:N, two (trimethyl silyl) aminopropyl ethyl diethoxy silanes of N-synthetic
Except using 38.6g 3-aminopropyl ethyl diethoxy silane as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (trimethyl silyl) aminopropyl ethyl diethoxy silanes of N-.
Synthesis example 10:N, two (trimethyl silyl) the amino butyl methyl diethoxy silanes of N-synthetic
Except using the amino butyl methyl diethoxy silane of 4-38.6g as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (trimethyl silyl) the amino butyl methyl diethoxy silanes of N-.
Synthesis example 11:N, two (the trimethyl silyl)-p-aminophenyl methyl dimethoxysilanes of N-synthetic
Except using p-aminophenyl methyl dimethoxysilane 38.6g as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (the trimethyl silyl)-p-aminophenyl methyl dimethoxysilanes of N-.
Synthesis example 12:N, two (trimethyl silyl) the amino undecyl methyldiethoxysilane of N-synthetic
Except using the amino undecyl methyldiethoxysilane of 37.1g 11-as the aminosilane position, be that benchmark carries out with synthesis example 1, obtain N, two (trimethyl silyl) the amino undecyl methyldiethoxysilane of N-.
Embodiment 1 (synthesizing of copolymer A)
Autoclave reactor to 5 liters of the internal volumes of nitrogen replacement adds hexanaphthene 2750g, tetrahydrofuran (THF) 41.3g, vinylbenzene 125g, 1,3-butadiene 375g.With after the temperature regulation to 10 of reactor content ℃, add n-Butyl Lithium 215mg, the beginning polymerization.Be aggregated under the adiabatic condition and implement, top temperature reaches 85 ℃.
When polymerisation conversion reaches 99%, append divinyl 10g, make its polymerization 5 minutes again.With after a small amount of application of sample of polymers soln is in the 30g cyclohexane solution that has added 1g methyl alcohol, add the N that obtains in the 1129mg synthesis example 1 by reactor, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-are carried out 15 minutes modified-reactions.Then, add 8.11g four (2-ethyl-1,3-hexylene glycol) titanium, restir 15 minutes.In reacted polymers soln, add 2,6 ditertiary butyl p cresol at last.Then, carry out desolventizing,, obtain copolymer A by the dry rubber of the hot-rolling of temperature adjustment to 110 ℃ by stripping.The polymerization formula of resulting copolymer A is shown in table 1-1, and its rerum natura is shown in table 2-1.
Embodiment's 2 (multipolymer B) is synthetic
Among the embodiment 1, four (2-ethyl-1,3-hexylene glycol) titanium is changed into (two-2,4-diacetylmethane) two propyl carbinol titaniums, in addition similarly to Example 1, obtain multipolymer B.The polymerization formula of resulting multipolymer B is shown in table 1-1, and its rerum natura is shown in table 2-1.
Embodiment's 3 (multipolymer C) is synthetic
Among the embodiment 1, change four (2-ethyl-1,3-hexylene glycol) titanium into four (2-Ethylhexyl Alcohol) titanium, in addition similarly to Example 1, obtain multipolymer C.The polymerization formula of resulting multipolymer C is shown in table 1-1, and its rerum natura is shown in table 2-1.
Embodiment's 4 (multipolymer D) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the 1-trimethyl silyl-2-oxyethyl group-2-methyl isophthalic acid-azepine-2-silicon pentamethylene that obtains in the synthesis example 2 into, in addition similarly to Example 1, obtain multipolymer D.The polymerization formula of resulting multipolymer D is shown in table 1-1, and its rerum natura is shown in table 2-1.
Embodiment's 5 (multipolymer E) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the 3-(2 that obtains in the synthesis example 3 into, 2,5,5-tetramethyl-(1-azepine-2,5-two silicon pentamethylene)-1-yl)-the propyl group methyldiethoxysilane, in addition similarly to Example 1, obtain multipolymer E.The composition of resulting multipolymer E is shown in table 1-1 and table 2-1 with transitivity.
Synthesizing of comparative example 1 (multipolymer F)
Except adding among the embodiment 1 beyond four (2-ethyl-1,3-hexylene glycol) titanium, similarly to Example 1, obtain multipolymer F.The polymerization formula of resulting multipolymer F is shown in table 1-1, and its rerum natura is shown in table 2-1.
Synthesizing of comparative example 2 (multipolymer G)
Among the embodiment 1, change four (2-ethyl-1,3-hexylene glycol) titanium into 2 ethyl hexanoic acid tin, in addition similarly to Example 1, obtain multipolymer G.The polymerization formula of resulting multipolymer G is shown in table 1-1, and its rerum natura is shown in table 2-1.
Synthesizing of comparative example 3 (multipolymer H)
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 4 into, two (trimethyl silyl) aminopropyl dimethylethoxysilane of N-, in addition similarly to Example 1, obtain multipolymer H.The polymerization formula of resulting multipolymer H is shown in table 1-1, and its rerum natura is shown in table 2-1.
Synthesizing of comparative example 4 (multipolymer I)
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change N-methyl-N-(trimethyl silyl) aminopropyl methyldiethoxysilane that obtains in the synthesis example 5 into, in addition similarly to Example 1, obtain multipolymer I.The polymerization formula of resulting multipolymer I is shown in table 1-1, and its rerum natura is shown in table 2-1.
Synthesizing of comparative example 5 (multipolymer J)
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 6 into, and N-dimethyl-3-aminopropyl methyldiethoxysilane in addition similarly to Example 1, obtains multipolymer J.The polymerization formula of resulting multipolymer J is shown in table 1-1, and its rerum natura is shown in table 2-1.
Synthesizing of comparative example 6 (multipolymer K)
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 7 into, and two (trimethyl silyl) aminopropyltriethoxywerene werene of N-in addition similarly to Example 1, obtain multipolymer K.The polymerization formula of resulting multipolymer K is shown in table 1-1, and its rerum natura is shown in table 2-1.
Embodiment's 6 (multipolymer L) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 8 into, two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-, in addition similarly to Example 1, obtain multipolymer L.The polymerization formula of resulting multipolymer L is shown in table 1-2, and its rerum natura is shown in table 2-2.
Embodiment's 7 (multipolymer M) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 9 into, two (trimethyl silyl) aminopropyl ethyl diethoxy silanes of N-, in addition similarly to Example 1, obtain multipolymer M.The polymerization formula of resulting multipolymer M is shown in table 1-2, and its rerum natura is shown in table 2-2.
Embodiment's 8 (multipolymer N) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 10 into, two (trimethyl silyl) the amino butyl methyl diethoxy silanes of N-, in addition similarly to Example 1, obtain multipolymer N.The polymerization formula of resulting multipolymer N is shown in table 1-2, and its rerum natura is shown in table 2-2.
Embodiment's 9 (multipolymer O) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 11 into, two (the trimethyl silyl)-p-aminophenyl methyl dimethoxysilanes of N-, in addition similarly to Example 1, obtain multipolymer O.The polymerization formula of resulting multipolymer O is shown in table 1-2, and its rerum natura is shown in table 2-2.
Embodiment's 10 (copolymer p) is synthetic
Among the embodiment 1, with N, two (trimethyl silyl) aminopropyl methyldiethoxysilane of N-change the N that obtains in the synthesis example 11 into, two (trimethyl silyl) the amino undecyl methyldiethoxysilane of N-, in addition similarly to Example 1, obtain copolymer p.The polymerization formula of resulting copolymer p is shown in table 1-2, and its rerum natura is shown in table 2-2.
Table 1-2
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
The modified conjugated diene base polymer L M N O P
Polymerization formula solvent: cyclohexane (g) contents of ethylene conditioning agent: oxolane (g) polymer monomer: styrene (g): butadiene (g) polymerization initiator: n-BuLi (mg) modifier: N-Si-8 * 12 (mg): N-Si-9 * 13 (mg): N-Si-10 * 14 (mg): N-Si-11 * 15 (mg): N-Si-12 * 16 (mg) condensation accelerator: Ti (EHDO)4 *8(g) 2750 41.3 125 375 215 987 - - - - 8.11 2750 41.3 125 375 215 - 1212 - - - 8.11 2750 41.3 125 375 215 - - - 1212 - - 8.11 2750 41.3 125 375 215 - - - - 1164 - 8.11- 2750 41.3 125 375 215 - - - - - 1791 8.11-
* 12.N, two (trimethyl silyl) aminopropyl methyl dimethoxysilanes of N-
* 13.N, two (trimethyl silyl) aminopropyl ethyl diethoxy silanes of N-
* 14.N, two (trimethyl silyl) the amino butyl methyl diethoxy silanes of N-
* 15.N, two (trimethyl silyl) p-aminophenyl methyl dimethoxysilanes of N-
* 16.N, two (trimethyl silyl) the amino undecyl methyldiethoxysilane of N-
Table 2-2
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
The modified conjugated diene analog copolymer L M N O P
Polymer molecule characteristic vinylbenzene key amount (%) contents of ethylene (%) mooney viscosity 20 55 40 20 55 34 20 55 38 20 55 33 20 55 33
Embodiment 11～20 and comparative example 7～12
Use the modified diene polymer A～P of the embodiment 6～10 shown in the embodiment 1～5 shown in the table 1-1, comparative example 1～6 and the table 1-2, according to the prescription shown in the table 31, the rubber combination that cooperates carbon black system by method modulation as follows, under 160 ℃ of conditions of 15 minutes, vulcanize, measure the rerum natura of vulcanized rubber.
Measurement result is shown in table 4-1 and table 4-2.In addition, among table 4-1 and the table 4-2, low exothermicity (tan δ: 50 ℃), antifriction consumption all are 100 exponential representation with comparative example 7, and the big more expression of numerical value is good more.
In addition, the polymer molecule characteristic of the modified diene polymer A～P shown in table 1-1 and the table 1-2 is shown in table 2-1 and table 2-2.
Table 3
Figure A20078003984700371
Annotate
* 1. modified conjugated diene base polymers: the polymkeric substance that uses table 1 record.
* 2. polyisoprene rubbers: JSR corporate system " IR2200 "
* 3. aromatic hydrocarbon oil: the emerging product corporate system of Fuji " ア ロ マ Star Network ス #3 "
* 4. carbon blacks: Mitsubishi Chemical Ind's system " ダ イ ヤ Block ラ Star Network N339 "
* 5. silicon-dioxide: eastern ソ one シ リ カ corporate system: " AQ "
* 6. silane coupling agents: デ グ Star サ corporate system " Si69 "
* 7. anti-aging agent 6C: the emerging chemical industrial company of imperial palace system " ノ Network ラ Star Network 6C "
* 8. accelerator D PG: the emerging chemical industrial company of imperial palace system " ノ Network セ ラ one D "
* 9. accelerator DMs: the emerging chemical industrial company of imperial palace system " ノ Network セ ラ one DM "
* 10. vulcanization accelerator NSs: the emerging chemical industrial company of imperial palace system " ノ Network セ ラ one NS-F "
Figure A20078003984700381
Table 4-2
Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20
The modified conjugated diene analog copolymer L M N O P
Sulfuration rerum natura (cooperation carbon black) tan δ (50 ℃) (index) wear resistant (index) 132 125 130 128 128 120 110 105 112 108
Embodiment 21～30 and comparative example 13～18
Use the modified diene polymer A～P of the embodiment 6～10 shown in the embodiment 1～5 shown in the table 1-1, comparative example 1～6 and the table 1-2, according to the formula I I shown in the table 3, cooperate silica-based rubber combination by method modulation shown below, vulcanize 160 ℃ of conditions of 15 minutes, measure the rerum natura of vulcanized rubber.
Measurement result is shown in table 5-1 and 5-2.In addition, among table 5-1 and the 5-2, low exothermicity (tan δ: 50 ℃), antifriction consumption all are 100 exponential representation with comparative example 13, and the big more expression of numerical value is good more.It the results are shown in table 5-1 and 5-2.
Table 5-2
Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30
The modified conjugated diene analog copolymer L M N O P
Sulfuration rerum natura (cooperation silicon-dioxide) tan δ (50 ℃) (index) wear resistant (index) 125 125 126 123 124 123 128 126 118 115
Be known as below by showing 4-1 and table 4-2, table 5-1 and table 5-2.
Comprise following modified conjugated diene polymer, cooperate the of the present invention rubber combination (embodiment 11～15) of carbon black as weighting agent, wherein, modified conjugated diene polymer of the present invention comprises by (a) and has protected primary amine groups at least and be combined in the operation that the compound of 2 functionality Siliciumatoms of the alkoxyl group on the Siliciumatom carries out modification; And (b) be that the operation that condensation accelerator carries out condensation reaction obtains by titanium, this rubber combination than comprising (a) operation but do not comprise (b) operation comparative example 7, comprise (a) operation but (b) the different comparative example 8 of the condensation accelerator of operation, comprise (b) operation but (a) the different comparative example 9～12 of the properties-correcting agent of operation, its low exothermicity (low-loss) and antifriction consumption are more excellent.
Especially, the comparative examples 9～12 different with properties-correcting agent are compared, and difference of them is remarkable.
The silicon-dioxide that the composition of table 5-1 and table 5-2 uses alternative carbon black is as weighting agent, even use silicon-dioxide also can obtain low exothermicity and antifriction consumption with the same excellence of carbon black as can be known.
Utilizability on the industry
Comprise the rubber constituent of rubber composition of the modified copolymer that obtains by manufacture method of the present invention and the interaction excellence of carbon black and/or silica, the dispersiveness of carbon black and/or silica can be improved, the excellent tires such as low exothermicity, destruction characteristic, antifriction consumption can be obtained. The tread-rubber that especially can effectively take tire as car with low combustion.

Claims (15)

1. the manufacture method of a modified conjugated diene polymer, it is characterized in that it has following operation: (a) make this reactive terminal of the conjugated diene polymer with reactive terminal and primary amino be protected in intramolecularly and comprise 1-oxyl and 1 reactive group is combined in the compound reaction of 2 functionality Siliciumatoms on the same Siliciumatom and the operation of carrying out modification; And (b) the titanium that comprises titanium compound be condensation accelerator in the presence of, the operation of carrying out the condensation reaction that aforementioned 2 functionality silicon compounds participate in.
2. the manufacture method of modified conjugated diene polymer according to claim 1; it also has following operation: (c) to the group reactive terminal that is combined in conjugated diene polymer, that come the compounds of the self-contained 2 functionality Siliciumatoms processing that is hydrolyzed, the protected primary amino in this group is converted to the deprotection operation of free amine group.
3. the manufacture method of modified conjugated diene polymer according to claim 1 and 2, the compound that comprises 2 functionality Siliciumatoms that uses in (a) operation are by the silicon compound of general formula (I) expression, by the silicon compound of general formula (II) expression and by the silicon compound of general formula (III) expression.
[Chemical formula 1]
Figure A2007800398470002C1
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
[Chemical formula 2]
Figure A2007800398470003C1
(in the formula, R 7～R 11The alkyl of representing carbonatoms 1～20 independently of one another, R 12The alkyl of the divalent of expression carbonatoms 1～12.)
[chemical formula 3]
Figure A2007800398470003C2
(in the formula, R 1, R 2The alkyl, the R that represent carbonatoms 1～20 independently of one another 3～R 5The alkyl, the R that represent carbonatoms 1～20 independently of one another 6Alkyl, the R of the divalent of expression carbonatoms 1～12 13Alkyl, the A of the divalent of expression carbonatoms 1～12 represent that reactive group, f represent 1～10 integer.)
4. the manufacture method of modified conjugated diene polymer according to claim 3, the A in the general formula (I) is the-oxyl of halogen atom or carbonatoms 1～20.
5. according to the manufacture method of each described modified conjugated diene polymer of claim 1～4, conjugated diene polymer with reactive terminal is to be polymerization starter with the organic alkali metal compound, makes conjugated diene compound separately or makes conjugated diene compound and the aromatic series vinyl compound carries out anionoid polymerization and obtains.
6. the manufacture method of modified conjugated diene polymer according to claim 5, conjugated diene compound be for being selected from 1,3-butadiene, isoprene and 2, in 3-dimethyl-1,3-butadiene at least a kind.
7. according to the manufacture method of claim 5 or 6 described modified conjugated diene polymers, aromatic ethenyl compound is a vinylbenzene.
8. according to the manufacture method of each described modified conjugated diene polymer of claim 5～7, the content of the polymerized unit of aromatic ethenyl compound is 0～55 quality % of conjugated diene polymer, and the vinyl bonds content of this conjugated diene polymer is 7～65 quality % of the polymerized unit of conjugated diolefine.
9. according to the manufacture method of each described modified conjugated diene polymer of claim 1～8, the condensation accelerator that (b) uses in the operation is at least a kind in the alkoxide, carboxylate salt and the methyl ethyl diketone complex salt that are selected from titanium or their mixing salt.
10. a modified conjugated diene polymer is characterized in that, it obtains by each described manufacture method of claim 1～9.
11. a rubber combination is characterized in that, comprises the described modified conjugated diene polymer of claim 10.
12. rubber combination according to claim 11, it comprises the rubber constituent of the aforementioned modified conjugated diene polymer more than the 15 quality % with respect to 100 mass parts, comprises the silicon-dioxide and/or the carbon black that amount to 20～120 mass parts.
13. rubber combination according to claim 12, rubber constituent constitutes by a kind in the multipolymer of the vinylbenzene that is selected from natural rubber, synthetic synthetic polyisoprene, divinyl rubber, styrene-butadiene rubber(SBR), ethene-alpha-olefin copolymer rubber, ethene-alpha-olefin-diene copolymer rubber, chloroprene rubber, halogenated butyl rubber and band halogenation methyl of the modified conjugated diene polymer of 15～100 quality % and 85～0 quality % and iso-butylene at least.
14. a pneumatic tyre is characterized in that, it uses each described rubber combination of claim 11～13.
15. a pneumatic tyre is used for each described rubber combination of claim 11～13 at any position of tyre surface, tread base and sidewall portion.
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